Corrugated fiberboard

ABSTRACT

Corrugated fiberboard which resists deterioration in strength when in the presence of moisture or water, and which has improved folding endurance. Such board is made by preliminarily treating medium and, optionally, liner members with a mixture of phenolaldehyde resole resin and polyvinyl alcohol (and/or polyvinyl acetate and/or partially hydrolyzed such materials) and thereafter fabricating corrugated fiberboard from the so-treated members using a waterproof adhesive system containing polyvinyl alcohol, polyvinyl acetate, and/or phenol-aldehyde resin.

United States Patent [72] Inventors John R. LeBlanc Wilbraham, Mass.; Robert W. Miller, Mentor, Ohio [21] Appl. No. 861,271 [22] Filed Sept. 26, 1969 [45] Patented Sept. 21, 1971 [73] Assignees Monsanto Company St. Louis, Mo. Alton Box Board Company Alton, lll. a part interest to each [54] CORRUGATED FIBERBOARD 10 Claims, 2 Drawing Figs.

[52] U.S.Cl 161/133, 117/155 L, 161/264, 260/29.3, 260/844 [51 Int. Cl B32b 3/28, B32b 27/42, C08g 37/18 [50] Field of Search 117/155 L; 161/133, 264; 260/293, 51.5, 840, 844

[56] References Cited UNlTED STATES PATENTS 3,004,941 10/1961 Mestdagh et a1 161/257 X 3,024,212 3/1962 Paschallet a1. 117/155 L Primary Examiner-Robert F. Burnett Assistant Examiner--Stephen M. Hoffman Attorneys-John W. Klooster, Arthur E. Hoffman, Richard W.

Sternberg and Neal W. Willis ABSTRACT: Corrugated fiberboard which resists deterioration in strength when in the presence of moisture or water, and which has improved folding endurance. Such board is made by preliminarily treating medium and, optionally, liner members with a mixture of phenol-aldehyde resole resin and polyvinyl alcohol (and/or polyvinyl acetate and/or partially hydrolyzed such materials) and thereafter fabricating corrugated fiberboard from the so-treated members using a waterproof adhesive system containing polyvinyl alcohol, polyvinyl acetate, and/or phenol-aldehyde resin.

PATENIEU SEP2I ISYI 3,607,598

TREAT LINER WITH TREAT MEDIUM TREAT LINER WITH RESIN (OPTIONAL) WITH RESIN RESIN (OPTIONAL) r I I E.) I DRY TO PRESET DRY TO PRESET DRY TO PRESET VOLATILES CONTENT VOLATILES CONTENT VOLATILES CONTENT rm in CORRUGATE'MEDIUM AND APPLT ADHESIVE T0 FLUTES THEREOF f j ASSEMBLE FIBERBOARD 8 HOT PRESS TO SET ADHESIVE AND (OPTIONALLY) RESIN MAKE CARTON BLANKS (SLOT, SCORE, CUT, ETC.)

HEAT TREAT BLANKS TO CURE RESIN (OPTIONAL) HUMIDIFY BLANKS F|G 2 (OPTIONAL) ASSEMBLE BLANKS INTO CARTONS INVENTORS ROBERT W. MILLER, JOHN R. LeBLANC ATTORNEY CORRUGATED FIBERBOARD BACKGROUND Corrugated fiberboard has been used for many years and for various purposes, but it is well known to have poor wet strength properties. Manufacturers of corrugated fiberboard have tried to improve board wet strength properties and in a few instances some success has been achieved in improving wet strength; however, it is typical to achieve wet strength only with a loss of fiberboard fold endurance (or flexibility). Such loss occurs primarily because, it is theorized, the resin systems used to improve wet strength cause embrittlement in the product board. Efforts, then, to improve corrugated fiberboard wet strength properties take into account the desirability of achieving improvement in wet strength without an undesirably great loss in fold endurance.

There has now been discovered a new type of corrugated fiberboard which not only has surprising and unexpected improvement in wet strength properties, but which has greatly improved fold endurance. Such fiberboard has its medium members, and, optionally, its linear members, treated with a particular mixed resin system, and the medium members are bonded to the liner members with an adhesive system which typically uses one of the polymers employed in the resin-treating system. Advantageously, such fiberboard can be produced economically using conventional corrugated fiberboardmanufacturing equipment.

Other and further advantages will be apparent to those skilled in the art from the present teachings.

SUMMARY The present invention relates to a novel corrugated fiberboard construction adapted to have good wet strength and crush resistance and to have improved folding endurance. For present purposes, wet strength and crush resistance of corrugated fiberboard may be conveniently measured comparatively using flat crush resistance data measured on corrugated fiberboard before and after moisture exposure by means of ASTM Test Procedure No. D-122554, and on containers made from such corrugated fiberboard using compression test procedures by means of ASTM Test Procedure No. D64247. Similarly, for present purposes, folding endurance may be measured using ASTM Test Procedure No. D-643-43.

Sheet members adapted for use in this invention as medium in the manufacture of the corrugated fiberboard utilize cellulosic paper ranging in thickness from about 7 to 15 thousandths of an inch and having basis weights of from about 25 to 36 pounds per 1,000 sq. ft. Such a paper has been treated with from about to 15 weight percent (dry weight basis) of a mixed polymer system as hereinafter described. The paper after such resin system treatment has a total volatiles content of from about 3 to weight percent.

The terms treated," treating, or treatment" as used herein are generic to both impregnation and coating of the substrate paper itself; such can be accomplished in any convenient, conventional manner, as hereinafter further detailed and illustrated.

Sheet members adapted for use in this invention as liners in the manufacture olthe corrugated fiberboard utilize cellulosic paper ranging in thickness from about 5 to 30 thousandths of an inch and having basis weights of from about 25 to 120 pounds per 1,000 sq. ft. Such a paper has, if treated, from about 2 to 10 weight percent (dry weight basis) of such mixed polymer system, and a total volatiles content of from about 3 to 10 weight percent. Liner shect members used in the corrugated fiberboard of this invention need not be, but preferably are, so treated with such mixed polymer system.

A corrugated fiberboard construction of this invention em ploys a treated medium, as above described, and a liner (preferably, though not necessarily, a treated one) as above described. Each such medium is corrugated and positioned adjacent to a liner member on one side thereof (preferably there is a liner in each side of a corrugated medium). Each LII liner is bonded to its adjoining medium at positions of mutual contact therebetween with a water-resistant adhesive system which contains at least one polymer used in the mixedpolymer-treating system above indicated. This adhesive system is interposed between such a liner sheet member and such a medium sheet member at such positions of mutual contact therebetween (typically by application to the tips of the corrugated medium flutes before board assembly).

The mixed-polymer-treating resin system used in this invention comprises (on a dry weight percent total basis):

A. from about 25 to 95 weight percent of a phenol-aldehyde resole resin characterized by having: I. a mol ratio of combined formaldehyde to phenol ranging from about 1.0 to 3.0, and

2. a water solubility such that at least about 30-weightpercent aqueous solution of resin solids can be prepared, and from about 5 to 75 weight percent of at least one polyvinyl polymer selected from the group consisting of polyvinyl acetate, partially hydrolyzed derivatives of polyvinyl acetate, ad substantially fully hydrolyzed polyvinyl alcohol, and each such polyvinyl polymer being further characterized by having a molecular weight such that an aqueous solution or colloidal dispersion (including latices, emulsions, etc.) thereof can be prepared initially which, at a polymer concentration of about 4 weight percent, has a viscosity of from about 5 to centipoises (cps).

In addition, such mixed-polymer-treating solution preferably contains (same basis) from about 0.2 to 5 weight percent of an ammonium salt ofa mineral acid.

Although phenol itself is generally employed in the formation of phenol-aldehyde resole resins as above described, other phenols known to the art are also suitable for use in this invention, such as lower alkyl substituted phenols (such as cresol, xylenol, etc. resorcinol, and the like; such other phenols as used are usually employed in combination with phenol itself. Similarly, although formaldehyde is generally employed as the aldehyde in the preparation of phenol-aldehyde resole resins as above described, other aldehydes known to this art are also suitable for use in the invention, such as acetaldehyde, and the like; such other aldehydes as used are usually employed in combination with formaldehyde.

The Phenol-Aldehyde Resins Phenol-aldehyde resole resins as described above are well known to the prior art. Resins of phenol and formaldehyde are preferred.

Thus, such phenol-formaldehyde resole resin useable in this invention can be prepared by condensing under aqueous liquid phase conditions from about 1.5 to 5 mols of aldehyde with each mol of phenol. Preferentially, the condensation is accomplished using an alkaline catalyst. The condensation is continued until a predetermined free formaldehyde content is reached, as determined, for example, by the hydroxylamine hydrochloride test. A suitable free-formaldehyde content is typically from about 3 to 15 weight percent based on total weight of starting reactants. The aldehyde used in the starting reactants can be in the ratio range of about 1.5 to 5 mols per mol of phenol, and, preferably one employs from about 1.5 to 3.6 mols of formaldehyde per mol of phenol. Typical condensation temperatures range from about 50 to 89 C. Typical basic catalysts include alkali metal hydroxides such as sodium hydroxide, or alkaline earth hydroxides such as calcium hydroxide, trialkyl amines, such as triethylamine, or the like. The product is a phenol-formaldehyde resol resin in aqueous solution having a total solids content typically from about 30 to 70 weight percent. Usually, and preferably, the resin solution is prepared as a concentrate of from about 40 to 55 weight percent solids (based on the total solution weight) which may be conveniently and preferably diluted down before use to a solids content of from about 5 to 50 weight percent. Preferably, the solids content of the concentrated ranges from about 45 to 60 weight percent, and preferably the solids content of the diluted working solution ranges from about to 45 weight percent.

For use in this invention, it has been found that a resole resin should preferably not be advanced in manufacture beyond the point where it has a water solubility such that about 30-weight-percent solids in aqueous solution thereof can be prepared (more preferably about 55 weight percent). Also, it has been found that this resole resin should have a methylol content per aromatic ring of from about 0.5 to 3 (more preferably from about 1 to 2.5) as determined, for example, by NMR measurements. Such a preferred resole appears to have better paper-treating characteristics, especially at the high application speeds conventionally employed for paper transport in the manufacture of corrugated fiberboard. In addition, it has been found that such a preferred resole resin should have a pH of from about 5.6 to 9.2 when in the form of an aqueous solution of about 35-weight-percent total resin solids (more preferably from about 7 to 8.5). Also, it has been found that such a preferred resole resin should have an ash content of less than about 2.5 weight percent based on about a 35 weight percent aqueous solution of total resin solids (more preferably less than about 0.7). Optionally, one can add an inorganic acid salt to such a preferred resin. Such addition preferably does not cause the pH of such a product resin system to fall outside the range of about 0.8 to 6. it will be appreciated by those skilled in the art that, in general, treatment of paper with resin will usually, as a matter of convenience, be accomplished as a separate, preliminary operation before boxboard manufacture is undertaken.

One convenient way in which to measure the ash content for present purposes is to take two grams of such an aqueous solution (35 percent solids) and deposit same in a crucible. The crucible is then heated to about 150 C. for about 2 hours to substantially completely cross link the resin and evaporate free water and thereafter the crucible is exposed to about 540 C. for about 24 hours. Afterwards, the crucible is cooled to room temperature and measured to determine an increase in weight over starting empty weight thereby giving the ash content of the resin.

The Polyvinyl Polymer Polyvinyl polymers as described above (including homopolymers and copolymers) are well known to the prior art and are well described in the literature, so no detailed description thereofis deemed necessary or desirable herein.

Preferred polyvinyl alcohols for use herein contain not more that about 10 weight per cent (based on total polymer dry weight) of residual ester groups, and a preferred polyvinyl acetate for use herein contains not more than about 75 weight percent (based on total polymer dry weight) of its acetate groups hydrolyzed. It will be appreciated that any partially hydrolyzed polyvinyl acetate (or incompletely hydrolyzed polyvinyl alcohol) as indicated above can be used in this invention.

The Paper As those skilled in the art will appreciate, in the art of corrugated fiberboard, it has been conventional to employ as the medium sheet member a semichemical cellulosic paper. A corrugated medium member is fon'ned by running a continuous sheet of medium through corrugating rolls. The medium, or 9 point" as it is sometimes called, takes on a wavelike shape as it passes between the corrugating rolls which mesh similar to gear teeth except that they are especially shaped to provide contours deemed best by a particular manufacturer for corrugations.

While the corrugating medium may be any of the cellulosic fibrous sheet materials conventionally used in the art, it is usually a sheet of about 26 pounds per 1,000 sq. ft. having a thickness of about 0.009 inch for all grades of combined TABLE I Number of Flutes Thickness of Trade per foot Single Wall Designation (approximate) Board, in.

A 33-39 (LIBS-(L2H) E -97 0 (MS-0.0624

Approximate, depending on thickness offacings and also the particular cnrrugat ing rolls.

As with medium sheet members, any conventional cellulosic liner sheet member can be used in the manufacture of the corrugated fiberboard of the present invention. Generally, the liner sheet members are made from sulfate Kraft, but sometimes are made from the pulps.

Kraft for liner sheet members is usually made of a Fourdrinier machine although some is made on a cylinder machine. Commonly, liner sheet members are made to standard weights, such as 26, 33, 38, 42, 47, 69, and 90 pounds per 1,000 square with thicknesses for such liner sheet members ranging from about 0.008 inch to 0.025 inch. Special linerboard can be used.

Details on the characteristics of medium sheet members and liner sheet members are well known to the corrugated fiberboard manufacturing industry. See, for example, Uniform Freight Classification Rule 41. The corrugation flutes can be combined using adhesive with a facing or liner sheet member on one side only, called a single face board; when facings are on both sides of the corrugated medium sheet member, the product is sometimes called single wallboard or double face board. If there are two sheets of flutes with a facing on each side and one in the middle, the product is sometimes called double wallboard. If there are three layers of flutes with two outer liner facings and two liner facings between medium layers, the product is sometimes called triple wallboard.

Paper Treatment The medium and liner can be treated with a mixed resin system by immersion or any other convenient coating techniques. In a product corrugated fiberboard, only the medium need be resin treated, but preferably, both liner and medium sheet members are resin treated. For example, in liner treatment, a preferred method involves surface coating rather than immersion impregnation. Suitable coating procedures involve application to one surface of a liner with a roller coater, doctor blade, or other application mechanism. Such a procedure is particularly applicable when only one side of a a resin is to be treated with a resin system because a coating procedure produces a differential impregnation or coating of the liner. Thus, the resin density is then greater relative to one surface of the resulting liner sheet than relative to the other (opposed) surface thereof. in general, it is preferred to uniformly coat medium sheet members with a resin system.

After treatment, a medium or liner sheet member is dried. Drying may, for example, be accomplished by passing such over or through a hot zone such that the temperature of the liner and/or the medium preferably does not exceed about 107 C. for more than about 0.] second so as to avoid thermosetting the resin system. In drying, water is substantially completely removed without appreciable advancement or curing of the resin impregnated into the liner or medium sheet member. Thus, the percentage of volatiles in a treated liner or medium is controlled within the range of about 3 to weight percent (total weight basis). For example, if the percentage of volatiles is reduced below such range, the resin system tends to cross-link and subsequently during corrugated fiberboard production reduced adhesive bonding to such a resin crosslinked medium or liner sheet tends to result, among other undesired results. On the other hand, for example, if the percent age of volatiles is left appreciably above such range, reduced adhesive bonding can likewise result. Also, outside of these ranges, a treated medium may be difficult to corrugate.

Adhesive Systems The adhesive systems used in this invention are well known to the prior art and employ at least one polymer selected from he group consisting of the phenol-aldehyde resole resins as described above and the polyvinyl polymers as described above and mixtures thereof. Such adhesive systems are well known to those of ordinary skill in the art.

In general, a given adhesive system employed in the products of this invention should have a water resistance after setting or curing sufficient to provide a postwater soak paperto-paper fiber-tearing bond. Such a water-resistant bond is conveniently measured after a l2hour (24 hours preferred) room temperature water soak between two 42-pound basis weight sheets, each about 12 thousandths of an inch thick, both sheets being bonded together using an adhesive application rate equivalent to about 4 pounds adhesive solids per 1,000 sq.ft. of paper surface, and permitting such adhesive application to such a pair of sheets bonded together therewith to dry in air for about 24 hours before such test commences. The sheets are bonded together after a wet adhesive application before any appreciable moisture loss of that adhesive system's water has occurred and before using the conventional or usual setting or curing conditions employed in the art for that adhesive system.

Typically, such an adhesive system may contain, for example, from about 2.5 to 35 weight percent (dry weight basis) of such a polymer as above described, the exact amount in any given system, of course, being dependent upon individual circumstances and preferences, as those skilled in the art will appreciate with the balance up to 100 weight percent being selected from a group consisting of supplemental binders, fillers, and adjuvants.

In the case of the phenol-aldehyde polymers, the art conventionally extends such with starch to make the desired water-resistant adhesives. One preferred class of adhesives for use in this invention is a phenol-starch-formaldehyde adhesive (more preferably a resorcinol-starch-formaldehyde adhesive. Preferably, the starch is partially reacted with the resin. Resole type phenolic resins are also preferred. Such adhesive systems for use in the present invention preferably have cure or set times not less than about 15 seconds at 170 C. An advantage of such adhesive systems from the standpoint of utilization in the present invention is that they characteristically display quick tack properties which make them suitable for corrugated fiberboard manufacture on high-speed equip ment.

A typical resorcinol-formaldehyde-starch adhesive system contain at least about 1 weight percent (based on total adhesive system solids) of combined formaldehyde, typically the average number ofcombined mols of formaldehyde per mol of phenol ranges from about 1.0 to 2.9, and typically such a system contains about 70 weight percent starch (based on total adhesive solids). Variations, of course, are possible without departing from the spirit and scope of this invention. Commonly, a supplier provides such an adhesive as a one or a two-tank formulation, which, in the latter case, are combined before use and typically are further diluted with water before actual use.

Another preferred class of adhesives for use in the present invention uses substantially fully hydrolyzed polyvinyl alcohol. The polyvinyl alcohol used therein characteristically and preferably has a molecular weight such that a 4 -weight-percent aqueous solution thereof has a viscosity at 20 C. of from about 40 to 70 centipoises, about 55 to 65 centipoises being more preferred. in general, the polyvinyl alcohol used should be substantially fully hydrolyzed by which reference is had to the fact that a given polyvinyl alcohol used contains not more than about 5 weight percent of residual ester groups (based on total polymer dry weight), and preferably not more than about 2 weight percent. Typically, such a preferred adhesive system can contain in addition to the polyvinyl alcohol supplemental binder materials, fillers, and adjuvants. in general, polyvinyl alcohol adhesive systems as above characterized can have the following composition:

Typical supplemental binders employed in the art include materials such as starch, dextrin, and synthetic polymeric materials, like phenol-aldehyde condensates, urea-formaldehyde condensates, polyvinyl acetate, polyacrylates, etc. Typical fillers employed in the art include materials such as clay, asbestos, mica, aluminum silicate pigments, wood floor, etc. Typical adjuvants employed in the art include fluidizing agents (such as urea, ammonium thiocyanate, etc. and com plexing agents such as those which improve tack or improve water insolubility, such as boric acid and other boron compounds. acidic metal salts having multivalent cations, or the like, Other adjuvants which can be employed as those skilled in the art will appreciate, include viscosity control aids; dyes and pigments; plasticizer and humectants; stabilizers; and bac tericides, germicides, fungicides, etc. and the like. It is preferred to employ polyvinyl alcohol adhesive systems which have quick tack characteristics. One quick tack-measuring procedure is described in column 3, lines 33 through 64 of US. Pat. No. 3,371,004; by this procedure, it is preferred to employ adhesive systems having a quick tack strength of from about 2.7 to 10.1 grams per square centimeter. Quick back is especially important in the single facer operation corrugated board manufacture.

Commonly, an adhesive system at the time of use to make corrugated fiberboard of this invention is in the form of an aqueous dispersion or mixed aqueous dispersion, aqueous solution, and aqueous dispersion/solution mixture having a total solids content of from about 15 to 35 weight percent (based on total system weight). Typical viscosities range from about 200 to 8,000 centipoises.

Detailed Description-Making Corrugated Board If not stored interveningly, Commercially treated medium and a liner member are combined together. commercially a conventional corrugating machine may be used for this operation.

Although an adhesive system as described above is generally discontinuously but automatically applied only to the flutes ofa corrugated treated medium when using machinery to make corrugated fiberboard of this invention, typical machine adhesive application rates range from about 3 to 12 pounds adhesive solids per 1,000 sq.ft. of product corrugated fiberboard but more or less than this amount can be employed. Adhesive application rates are not critical and can be widely varied without departing from the spirit and scope of this invention.

After adhesive application, corrugated medium sheet member (s) and liner sheet member(s) are duly combined together, as in a so-called corrugating machine, into board, the resulting fiberboard construction is subjected to temperatures of from about 160 to 235 C. for times of from about seconds to 5 minutes (200 to 225 C. for 5 to 30 seconds preferred) to substantially set the adhesive. Such a product is converted to one of this invention by heating such to usually somewhat higher temperatures and for times sufficient to sub stantially completely thermoset the phenol aldehyde resole resin system in the treated paper of the board. Such setting of adhesive and thermosetting of treating resin can be accomplished in a single step, or in two steps, all as hereinafter further described and illustrated. Preferably, a corrugated fiberboard construction of this invention has two liner sheet members.

Usually, and conventionally, a corrugated fiberboard of this invention is promptly made into box blanks following manufacture, through it is possible and convenient to store the corrugated fiberboard before same is used to make box blanks. Box (or carton) blank manufacture is well known to those of ordinary skill in the art and does not form part of this invention. Conventional box blanks manufacture includes scoring, slotting, and slitting.

If the corrugated fiberboard used to make the blanks does not have its resin-treated medium and (optionally) liner members thermoset, a final blank-processing step is performed. Thus, in such event, usually before a blank is formed into a box, but after scoring, slotting and related operations are completed, a resulting carton blank is heated to a temperature and for a time sufficient to substantially completely thermoset the phenol-aldehyde resin system impregnated into the medium and (optionally) liner members of the board. In general, suitable temperatures for this purpose range from about 160 to 235 C. applied for times ranging from about 2 to minutes (with higher temperatures requiring shorter cure times). Such a thermosetting increases the water-resistance properties (e.g. crush resistance, as indicated above) of the corrugated fiberboard and blanks made therewith.

DESCRIPTION OF DRAWINGS The invention is better understood by reference to the attached drawings wherein:

FIG. 1 is an enlarged, diagrammatic vertical cross-sectional view, some parts thereof broken away, of one embodiment of a corrugated fiberboard construction of this invention, and

FIG. 2 is a simplified flowsheet illustrating the method of making corrugated fiberboard in accordance with the teachings of the present invention.

Turning to FIG. 1, there is seen a corrugated fiberboard construction of the present invention which is designated in its entirety by the numeral 10. Construction 10 is seen to incorporate a pair of facing liner sheet members 11 and 12. Interposed between liner sheet members 11 and 12 is a corrugated medium sheet member IS. The liner sheet members 11 and 12 are optionally, but preferably, treated with a phenol-aldehyde resole resin as taught herein above, while the medium sheet member 13 is treated with a phenol-aldehyde resole resin as taught herein above.

The tips of the flutes in the corrugated medium 13 are bonded to the adjacent faces of respective liner members 11 and [2 by means of polyvinyl-alcohol-based adhesive system 14 as taught herein. conventionally, the adhesive 14 is applied to the tips of the flutes during the combining operation of the medium 13 and the liners 11 and 12. After assembly, the construction 10 is heated as above described to set the adhesive 14 and produce the corrugated fiberboard 10.

Steps in one embodiment of a process for making a fiberboard 10 are shown in FIG. 2. This block diagram is believed to be largely self-explanatory particularly in view of the foregoing description so no detailed explanation thereof is given herein. Observe that FIG. 2 merely illustrates one mode of practicing the present invention and that deviations and variations in accordance with the teachings of the present invention are possible without departing from the spirit and scope of this invention.

The machine used to make corrugated fiberboard usually combines into a single operation the steps of corrugating the medium, applying adhesives to the flutes thereof, and assembling the so-prepared medium with liner. Hot-pressing of the so-assembled fiberboard is usually also accomplished in the same machine. Although the process embodiment of FIG. 2 discloses initially curing only the adhesive, it will be appreciated that it is convenient to practice the invention by curing both the adhesive and the resin for treatment of medium and liner members before exposing a product corrugated fiberboard to high moisture conditions.

Those skilled in the art will appreciate that the type of corrugated fiberboard shown in FIGS. 1 and 2 is known to the trade as double-faced corrugated fiberboard since a medium sheet is combined with a so-called inner and so-called outer liner.

Single-faced corrugated fiberboard is made by using a single-corrugated medium member and a single liner member; double-wall corrugated fiberboard comprises three liners with two corrugated medium members alternatively spaced between the liners; a triple-wall corrugated fiberboard comprises seven thicknesses and is made by bonding two singlefaced boards into a double'faced board in which there are four liners and three corrugated medium members. All such corrugated fiberboard constructions are within the contemplation of the present invention.

Embodiments The following examples are set forth to illustrate more clearly the principles and practice of this invention and to one skilled in the art and they are not intended to be restrictive but merely to be illustrative of the invention herein contained. All parts are parts by weight unless otherwise indicated.

The following examples illustrate mixed resin systems and adhesive systems suitable for use in making products of this invention. Each such system has characteristics as above indicated as being useful in the manufacture of the products of this invention.

Example A A treating resin is prepared as follows:

To parts of phenol in a reaction kettle are added first parts of 50-percent formalin and then 4 parts of sodium hydroxide sufficient to bring the pH to about 8.6. The mixture is refluxed for about 4 hours at about 65 C., while maintain ing a reaction pH of about 8.6. Thereafter, this mixture is cooled to about 40 C. This mixture is then neutralized to a pH of about 7.0 with aqueous diluted hydrochloric acid. The resulting mixture is dehydrated under vacuum to the desired solids level (see table A below). The product yield is about 270 weight percent based on starting phenol. The product has a water solubility such that a 55-weight-percent aqueous solution of resole resin solids can be prepared. The resin characteristics are summarized in table A below.

Fifty parts by weight of polyvinyl alcohol having a residual acetate content of less than 2 percent by weight and a 4 percent aqueous solution viscosity of 63 centipoises at 20 C. is dry blended with 3 parts of powdered glyoxal. The dry blend is dispersed in 950 parts of cold water and the slurry is heated to 95 C. while maintaining agitation to dissolve components. The solution is then cooled to room temperature.

To I00 parts by weight of the phenol-formaldehyde resin above prepared are added 200 parts by weight of the polyvinyl alcohol solution with agitation Example B A treating resin is prepared as follows:

To 100 parts of phenol in a reaction kettle are added first 170 parts of SO-percent formalin and the 6 parts of calcium hydroxide sufficient to bring the pH to about 8.6. The mixture is refluxed for about 4 hours at 62 C. Thereafter, the mixture is cooled to 40. The mixture is then neutralized to a pH of 7.2 with carbon dioxide. The resin is filtered to remove the calciurn carbonate. The product has a water solubility such that a 55-weight-percent percent aqueous solution of resole resin solids can be prepared. The resin characteristics are summarized in table A below.

A 55 percent solids content polyvinyl acetate homopolymer emulsion produced by polymerizing vinyl acetate in water is prepared having a specific gravity at 20 C. of about 1.1; this material is available commercially under the trade designation Gelva Emulsion S-55 from Monsanto Company.

To 100 parts by weight of the phenol-formaldehyde resin above prepared are added 35 parts by weight of the polyvinyl acetate emulsion with agitation.

Example C A treating resin is prepared as follows:

To 100 parts phenol in a reaction kettle are added 150 parts of SO-percent formalin and 4 parts triethylamine amine as a catalyst. The mixture is refluxed at about 70 C. for about 4 hours until a free formaldehyde end point of 8.6 percent is reached. The resin product is then cooled to 30 C. lt has a solids content of about 48.0 weight percent. The product has a water solubility such that a 55-weight-percent aqueous solution of resole resin solids can be prepared. The resin characteristics are summarized in table A below.

Independently, a polyvinyl acetate homopolymer emulsion as described in example C above is partially hydrolyzed using sulfuric acid as catalyst and heat until about 7 weight percent of the acetate groups are hydrolyzed to polyvinyl alcohols thereby providing potential cross-linking sites on polyvinyl acetate molecules.

To 100 parts by weight of the phenol-formaldehyde resin above prepared are added 100 parts by weight of the aboveprepared partially hydrolyzed polyvinyl acetate emulsion with agitation.

Example D A treating resin is prepared as follows:

To 100 parts by weight of a sample of the resole resin of example A above are added 100 parts by weight of polyvinyl alcohol solution prepared as in example A above but without glyoxal, and 50 parts by weight of the polyvinyl acetate homopolymer emulsion described in example 8 above with agitation.

TABLE A Example A Example B Examplc C Total resin solids in aqueous solution 55 50 48 Free formaldehyde 9 6 8.5 H" 7 7.2 8.0 Combined average moles formaldehyde per aromatic ring" 2.25 2.25 2.15 Ash content 2.3 0.3

Free formaldehyde Content determined by the so-called hydroxylamine hydrochloride method.

1 pH measured at 25' C. using an aqueous solution of about 35 weight percent total resin solids.

1 Measured by methylol content and methylene bridges per aromatic ring using nuclear magnetic resonance on a sample of product.

Ash content determined using a 35 weight percent aqueous solution of total resins at 150 C. at 2 hours and thereafter pyrolyzed for 24 hours at 540 C.

Example E A treating resin is prepared as follows: To 100 parts of phenol in a reaction kettle are added first 133 parts of SO-percent formalin and then 2.5 parts of sodium hydroxide. The mixture is refluxed to a free formaldehyde content of about 4.2 percent. Thereafter. this mixture is cooled to about 40 C. This mixture is then neutralized to a pH of about 8.0 with aqueous diluted hydrochloric acid. The resulting mixture is dehydrated under vacuum to a resins solids level of about 60 weight percent.

A 55-percent solids polyvinyl acetate homopolymer emulsion having a viscosity of 1,200 cps. and prepared using a polyvinyl alcohol protective colloid if further modified by blending with a S-percent solution of a polyvinyl alcohol having a residual acetate content of about 21 weight percent and an aqueous solution viscosity of 53 cps. when measured as a 4- percent solution at 20 C. The resulting product has a solids content of 40 percent.

To parts by weight of a sample of the resole resin above prepared are added 100 parts by weight of the polyvinyl alcohol, polyvinyl acetate mixture above prepared with agitation.

Example F A polyvinyl alcohol adhesive as described in example 1 of US. Pat. No. 3,324,065 is prepared.

Example G A polyvinyl alcohol adhesive as described in example 1 of US. Pat. No. 3,320,200 is prepared.

Example H A polyvinyl alcohol adhesive as described in example 2 of US. Pat. No. 3,135,648 is prepared.

Example 1 A polyvinyl alcohol adhesive as described in example 2 (column 4, lines 40 -64 of US. Pat. No. 3,371,004 is prepared.

Example .1

A resorcinol-starch-formaldehyde adhesive system for use in this invention is prepared as follows:

To gallons of water is added 142 pounds of a commercially available resorcinol-starch mixture (from Penick and ord under the trade designation Douglas Waterproof Corrugating Adhesive 07) and 150 pounds of corn starch.

The resulting mixture is heated to from about to 145 F. for 10 minutes at which time there is added thereto additionally 10 gallons of water and 20 pounds of caustic (sodium hydroxide). This last mixture is agitated for an additional 10 minutes thereafter at an elevated temperature of about 140 F. Finally, to the resulting mixture is added an additional 80 gallons of water. The product constitutes what can be termed the primary mixture, or carrier portion, of the adhesive system.

Next is prepared the secondary mixture of raw starch portion, as follows:

To 250 gallons water is added 1,000 pounds of corn starch and 68 pounds of 37-percent aqueous formaldehyde. The composition is mixed at room temperature.

Finally, the primary mixture and the secondary mixture are admixed together and stirred for about 1 hours. The product is an adhesive system ready for use. The is adhesive system has a total resorcinol to total starch weight ratio (based on total adhesive system solids) of from about 1 to 7, and it contains about 1.0 weight per cent (based on total adhesive system solids) of combined formaldehyde, as well as about 70-weightpercent (based on total adhesive systems solids) of starch. It has a total adhesive solids content of about 25 weight percent, a viscosity of about 1,000 centipoises and a gel point of about F. determined by heating the adhesive in a water bath heated gradually to the gel temperature.

Example K A phenol-formaldehyde-starch adhesive system for use in this invention is prepared as follows:

To 16 weight parts of water is added parts of the phenolformaldehyde resin prepared as described in example E above, 2.1 parts of a 23-percent caustic (sodium hydroxide) solution, and 4.4 parts of corn starch.

The resulting mixture is heated to 155 165 F. with continuous mixing and mixed an additional -20 minutes at 155 165 F. Finally, 13 parts of cooling water is added to the mix ture. This product constitutes what can be termed the primary mixture, or carrier portion of the adhesive system.

Next is prepared the secondary mixture or raw starch portion as follows:

To 41 parts water is added 18 parts corn starch. The composition is mixed at room temperature.

Finally, the primary mixture and the secondary mixture are admixed together and stirred for about 1 hour. The product is an adhesive system ready for use. The adhesive system has a total phenolic resin to total starch weight ratio (based on total adhesive system solids) of from about 1 to 8.6 lt has a total adhesive solids content of about 25 percent, a viscosity of about 800 cps, and a gel point of about 148 F., as determined by heating the adhesive in a water bath heated gradually to the gel temperature.

The following examples illustrate the manufacture of corrugated fiberboard of the present invention using the abovedescribed resole resins and adhesive systems.

Example 1 Each side of a 26-pound basis weight medium paper sheet about 0.009 -inch thick are roller coated with aminoplast containing phenol-aldehyde resin system of example A to a total resins content of about 8 weight percent based on the dry weight of the sheet plus resin. One side of a 42 pound basis weight Kraft liner paper sheet about 0.012 inch thick is roller coated with the same resin system to a on resins content of 4 per cent based on the dry weight of the sheet plus resin. The so-treated medium sheet and liner sheet are each dried to a total volatiles content of about 6 percent (as indicated by drying the paper to 160 C. for 10 minutes to determined weight loss).

Next, a medium sheet as so prepared is corrugated into Type B flutes of about 50 per foot, and the polyvinyl alcohol adhesive of example F is applied to the tips of the flutes of the medium corrugations at the rate of about 8 pounds adhesive solids per 1,000 ft. of product fiberboard. This medium is then combined with two pieces of such liner sheet as prepared above one on each side of the adhesive-treated medium sheet so as to form a corrugated fiberboard. This board is not exposed to a temperature of about 160 C. for about 10 second to dry and thermoset the adhesive. This product can be considered to be an intermediate corrugated fiberboard product which may be converted as herein below described into a corrugated fiberboard product of this invention.

One portion of this intermediate product board is exposed to about 180 C. for about 4 minutes to thermoset the treating resin, and thereby produce product corrugated fiberboard of this invention. This fiberboard is then converted into a first set of box blanks by cutting, slotting and scoring.

A second portion of this intermediate product board is converted into a similar but second set of box blanks by cutting, slotting, and coring. These blanks are then exposed to about 180 C. for about 4 minutes to thermoset et the treating resin and thereby produce product corrugated fiberboard of this invention.

The first and the second box blanks are then formed into containers, and each such respective container is compression tested for dry and wet strength (top to bottom) using ASTM Test Procedure No. D-642-47. A container of similar dimensions is made from a blank composed of conventional untreated medium and liner members and the adhesive of example H. The compression tests are conducted on containers which are exposed before testing to 50-percent relative humidity for 24 hours at about 22 C. and also to a water immersion for 24 hours at about 22 C. The results show that the treated containers retain 30 to 40 percent of their original compression strength after water immersion whereas the untreated containers retain substantially no compression strength after water immersion.

Samples of corrugated board from the first box blanks, and samples of corrugated board from the second box blanks are tested, alone with samples of corrugated board from the untreated box blanks, for flat crush resistance before and after water immersion using ASTM Test Procedure D-l225-54. The results show that the treated board retains substantial strength after water immersion whereas the untreated board retains substantially no strength after water immersion.

Example 2 Using the procedure employed in example 1 to make the second blanks of the example, but instead employing as the medium one having Type C flutes and using a 33-pound basis weight paper 0.011 inch thick having a IO-Weighbpercent treating resin content and a 7-percent volatiles content, and further employing as the liner a 69-pound basis weight paper 0.018 inch thick having a 5-weightpercent treating resin content and an 8-percent volatiles content, blanks and then containers are made and similarly compression tested (top to bottom). The containers display excellent compression strength after water immersion. Samples of the corrugated board used in such blanks are similarly (example 1) evaluated for flat crush resistance and are found to have excellent flat crush resistance after water immersion.

Example 3 Using the procedure employed in example 1 to make the second blanks of that example, but instead employing as the medium one having Type C flutes and using a 33-pound basis weight paper 0.009 inch thick impregnated with 10 weight percent of the resin treating solution of example E and dried to a S-percent volatiles content, and instead employing an untreated liner paper having a l2-pound basis weight and a thickness of 0.012 inch. The product board is heated to 200 C. for 3 seconds, and then is cut. scored and slotted to form a box blank. The product blank is heated in a forced draft oven for 2 minutes at 200 C. to complete resin curing The product blanks are formed into containers and evaluated for compression strength as in example 1. and board used in the blanks is evaluated for flat crush resistance as in example 1. The results show the product board and blank to have excellent flat crush resistance and excellent compression strength, respectively, after water immersion.

Examples 4-12 12 Using the procedure employed in example 1 to make the first board and blanks there described, a series of corrugated box blanks are made, and evaluated as in example 1. in each case, the medium, the liner, the treating resin and the adhesive are as described in table 4 below. The corrugated board and blanks made therefrom display excellent crush resistance after basis weight of from about 33 to 120 ft., D. as a bonding composition, a water-resistant adhesive system employing at least one polymer selected from the pounds per 1,000 sq.

water immersion when evaluated by the procedures described group consisting of said phenol-aldehyde resole resin in example 1 above. systems, and said polyvinyl polymers,

TABLE 4 Medium 1 Liner Treating resin system Adhesive Amount in Amount in medium ner Amount Thickness Basis Thickness Basis Ex Percent Percent Percent Percent Ex. adhesive Ex. N0. (in inches) weight (in inches) Weight No. resin v resin vol. N0. applied 3 .009 26 .020 69 B 12 8 3 5 G 6 .011 33 .020 69 C 6 7 8 H 6 .011 33 .020 69 D 12 7 I 6 009 26 020 69 A 12 8 3 5 J 6 .009 26 .020 69 E 11 5 5 5 K 6 l Flutes in corrugated medium are Type B (about 50 per foot). 1 Pounds adhesive solids/1,000 It. 01 product board.

What is claimed is:

l. A corrugated fiberboard construction adapted to be rigid when wet comprising:

A. As a medium, a corrugated cellulosic sheet member having a thickness of from about 7 to 15 thousanths of an inch and a basis weight of from about 25 to 36 pounds per 1,000 sq. ft., said sheet member containing from about 5 to 15 weight percent (dry weight basis) of a mixed resin system and said sheet member having a total volatiles content of from about 3 to 10 weight percent,

B. said mixed resin system comprising (on a 100 parts by weight dry basis):

1. from about 25 to 95 weight per cent a phenolaldehyde resole resin system characterized by having: a. a mol ratio of combined formaldehyde to phenol ranging from about 1.0 to 3.0, and b. a water solubility such that at least about a 30- weight-percent aqueous solution of resin solids can be prepared, and 2. from about 5 to 75 weight percent of at least one polyvinyl polymer selected from the group consisting of: polyvinyl acetate, partially hydrolyzed derivatives of polyvinyl acetate, and substantially fully hydrolyzed polyvinyl alcohol, and each such polyvinyl polymer being further characterized by having a molecular weight such that an aqueous solution or colloidal dispersion (including latices, emulsions, etc.) thereof can be prepared initially which, at a polymer concentration of about 4 weight percent, has a viscosity of from about 5 to 125 cps., C. as a liner, a cellulosic sheet member having a thickness of from about 5 to thousandths of an inch and having a B. said corrugated medium sheet member being positioned adjacent said liner sheet member and being bonded thereto at positions of mutual contact therebetween by said bonding composition, and

F. such resulting construction having been subjected to a temperature of from about to 235 C. for times of from about 0.5 seconds to 5 minutes.

2. A construction of claim 1 which has been subjected to temperatures and times sufficient to substantially completely thermoset said phenol-aldehyde resin systems.

3. A box blank prepared from a corrugated fiberboard construction of claim 1.

4. A box blank prepared from a corrugated fiberboard construction of claim 3.

5. The box blank of claim 3 wherein said blank has been subjected to temperatures and times sufficient to substantially completely thermoset said phenol-aldehyde resin system.

6. A construction of claim 1 wherein said liner member is treated with from about 2 to 10 weight percent (dry weight basis) with a said phenol-aldehyde resin and has a total volatiles content offrom about 3 to 10 weight percent.

7. A construction of claim 6 which has been subjected to a combination of temperatures and times sufficient to substantially completely thermoset said phenol-aldehyde resin system.

8. A construction of claim 1 wherein said tion contains starch.

9. A construction of claim 1 wherein said bonding composition comprises a resorcinol-formaldehyde-starch adhesive system.

10. A construction of claim 1 wherein said bonding composition comprises a polyvinyl alcohol adhesive system.

bonding composi- 

2. from about 5 to 75 weight percent of at least one polyvinyl polymer selected from the group consisting of: polyvinyl acetate, partially hydrolyzed derivatives of polyvinyl acetate, and substantially fully hydrolyzed polyvinyl alcohol, and each such polyvinyl polymer being further characterized by having a molecular weight such that an aqueous solution or colloidal dispersion (including latices, emulsions, etc.) thereof can be prepared initially which, at a polymer concentration of about 4 weight percent, has a viscosity of from about 5 to 125 cps., C. as a liner, a cellulosic sheet member having a thickness of from about 5 to 20 thousandths of an inch and having a basis weight of from about 33 to 120 pounds per 1,000 sq. ft., D. as a bonding composition, a water-resistant adhesive system employing at least one polymer selected from the group consisting of said phenol-aldehyde resole resin systems, and said polyvinyl polymers, E. said corrugated medium sheet member being positioned adjacent said liner sheet member and being bonded thereto at positions of mutual contact therebetween by said bonding composition, and F. such resulting construction having been subjected to a temperature of from about 160* to 235* C. for times of from about 0.5 seconds to 5 minutes.
 2. A construction of claim 1 which has been subjected to temperatures and times sufficient to substantially completely thermoset said phenol-aldehyde resin systems.
 3. A box blank prepared from a corRugated fiberboard construction of claim
 1. 4. A box blank prepared from a corrugated fiberboard construction of claim
 3. 5. The box blank of claim 3 wherein said blank has been subjected to temperatures and times sufficient to substantially completely thermoset said phenol-aldehyde resin system.
 6. A construction of claim 1 wherein said liner member is treated with from about 2 to 10 weight percent (dry weight basis) with a said phenol-aldehyde resin and has a total volatiles content of from about 3 to 10 weight percent.
 7. A construction of claim 6 which has been subjected to a combination of temperatures and times sufficient to substantially completely thermoset said phenol-aldehyde resin system.
 8. A construction of claim 1 wherein said bonding composition contains starch.
 9. A construction of claim 1 wherein said bonding composition comprises a resorcinol-formaldehyde-starch adhesive system.
 10. A construction of claim 1 wherein said bonding composition comprises a polyvinyl alcohol adhesive system. 